Self-Assembly of Benzimidazole-Derived Tris-NHC Ligands and AgI-Ions to Hexanuclear Organometallic Cages and Their Unusual Transmetalation Chemistry |
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Authors: | Rajeev C Nishad Dr Arnab Rit |
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Institution: | Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600036 India |
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Abstract: | Multi-ligand self-assembly to attain the AgI-N-heterocyclic carbene (NHC)-built hexanuclear organometallic cages of composition Ag6( 3 a , b )4](PF6)6 from the reaction of benzimidazole-derived tris(azolium) salts H3- 3 a , b ](PF6)3 with Ag2O was achieved. The molecular structures of the cages were established by X-ray diffraction studies along with NMR and MS analyses. The existence of a single assembly in solution was supported by diffusion-ordered spectroscopy (DOSY) 1H NMR spectra. Further, transmetalation reactions of these self-assembled complexes, Ag6( 3 a , b )4](PF6)6, with CuI/AuI-ions provided various coinage metal-NHC complexes having diverse molecular compositions, which included the first example of a hexanuclear CuI-dodecacarbene complex, Cu6( 3 b )4](PF6)6. |
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Keywords: | DFT studies N-heterocyclic carbenes self-assembly supramolecular chemistry transmetalation |
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